Controlled monodefluorination and alkylation of C(sp<sup>3</sup>)–F bonds by lanthanide photocatalysts: importance of metal–ligand cooperativity
Amy E. Kynman, Luca K. Elghanayan, Addison N. Desnoyer, Yan Yang, Laurent Sévery, Andrea Di Giuseppe, T. Don Tilley, Laurent Maron, Polly L. Arnold
Abstract
with alkenes; addition of magnesium dialkyls enables catalytic C-F bond cleavage and C-C bond formation by all the complexes. Mechanistic experiments confirm the essential role of the Lewis acidic metal and support an inner-sphere mechanism of C-F activation. Computational studies agree that coordination of the C-F substrate is essential for C-F bond cleavage. The unexpected catalytic activity for all members is made possible by the light-absorbing ability of the redox non-innocent ligands. The results described herein underscore the importance of metal-ligand cooperativity, specifically the synergy between the metal and ligand in both light absorption and redox reactivity, in organometallic photocatalysis.